JP6843247B2 - Curable composition for imprint, cured product, pattern manufacturing method, lithography method, pattern, and polymerizable composition for imprint - Google Patents

Description

The present invention relates to a curable composition for imprinting, a cured product, a pattern manufacturing method, a lithography method, a pattern, a mask for lithography, and a polymerizable composition for imprinting.

The imprint method is a technique for transferring a fine pattern to a material by pressing a mold (generally called a mold or stamper) on which a pattern is formed. Since it is possible to easily produce a precise fine pattern by using the imprint method, it is expected to be applied in various fields in recent years. In particular, nanoimprint technology for forming nano-order level fine patterns is drawing attention.
As the imprint method, a method called a thermal imprint method or an optical imprint method has been proposed from the transfer method. In the thermal imprint method, a mold is pressed onto a thermoplastic resin heated to a temperature equal to or higher than the glass transition temperature (hereinafter, may be referred to as “Tg”), and the mold is released after cooling to form a fine pattern. Although various materials can be selected in this method, there are problems that high pressure is required at the time of pressing and that it is difficult to form a fine pattern due to heat shrinkage or the like.

On the other hand, in the optical imprint method, the mold is photo-cured in a state where the mold is pressed against the curable composition for imprint, and then the mold is released. Since it is imprinted on an uncured material, it is not necessary to heat it at high pressure or high temperature, and it is possible to easily form a fine pattern.
In the optical imprint method, a curable composition for imprint is applied onto a substrate (which is subjected to adhesion treatment if necessary), and then a mold made of a light-transmitting material such as quartz is pressed against the substrate. The curable composition for imprinting is cured by light irradiation while the mold is pressed, and then the mold is released to prepare a cured product to which the desired pattern is transferred.
Examples of the method of applying the curable composition for imprinting on the substrate include a spin coating method and an inkjet method. In particular, the inkjet method is an application method that has attracted attention in recent years from the viewpoint of reducing the loss of the curable composition for imprinting.

Further, a method of performing microfabrication using the transferred imprint pattern as a mask is called nanoimprint lithography (NIL), and is being developed as a next-generation lithography technology that replaces the current ArF immersion process. Therefore, the curable composition for imprint used in NIL is capable of resolving ultrafine patterns of 30 nm or less, similar to extreme ultraviolet (EUV) resists, and is highly etched as a mask for microfabrication of the object to be processed. Resistance is required. In addition, since throughput (productivity) is also important during mass production, nanoimprint suitability such as pattern filling property (shortening of filling time) and mold releasability (shortening of mold release time) is also required.

Patent Documents 1 to 6 are known as disclosure of a curable composition for imprint having excellent etching resistance, filling property and releasability. In Patent Documents 1 to 3, phenylethylene glycol diacrylate is used as an acrylate monomer having high etching resistance. Further, in Patent Document 4, a polyfunctional acrylate containing at least one of an alicyclic structure and an aromatic ring structure is used. Further, in Patent Documents 5 and 6, an acrylate monomer containing silicon is used in order to improve the etching resistance.

JP-A-2015-179807 Japanese Unexamined Patent Publication No. 2016-29138 Japanese Unexamined Patent Publication No. 2016-30829 Japanese Unexamined Patent Publication No. 2013-189537 Japanese Unexamined Patent Publication No. 2011-251508 Japanese Unexamined Patent Publication No. 2015-1330535

However, as a result of a detailed examination of the above document by the present inventor, when imprint lithography is performed using the curable composition for imprint described in the above document, the adhesion to the substrate may be insufficient or the imprint may be inadequate. It has been found that the storage stability of the curable composition for printing itself may be inferior.
An object of the present invention is to solve the above-mentioned problems, and to obtain a curable composition for imprint, which has high adhesion to a substrate when made into a cured product and has excellent storage stability. It is an object of the present invention to provide a cured product, a pattern manufacturing method, a lithography method, a pattern, a mask for lithography, and a polymerizable composition for imprinting.

式（１）中、Ｒ^１およびＲ^２は、それぞれ独立に、水素原子または炭素数１〜８の有機基であり、互いに結合して環を形成していてもよい；Ｒ^３は１価の有機基である；Ｒ^４およびＲ^５は、それぞれ独立に、水素原子または１価の有機基である。
＜２＞ 上記式（１）で表される化合物の含有量が、上記式（１）で表される化合物以外のラジカル重合性化合物の含有量１００質量部に対して、０．００５〜１質量部である、＜１＞に記載のインプリント用硬化性組成物。
＜３＞ 上記式（１）で表される化合物以外のラジカル重合性化合物は、(メタ)アクリロイル基の少なくとも１種を含む、＜１＞または＜２＞に記載のインプリント用硬化性組成物。
＜４＞ 上記式（１）で表される化合物の分子量が１００〜１５００である、＜１＞〜＜３＞のいずれか１つに記載のインプリント用硬化性組成物。
＜５＞ 上記式（１）で表される化合物が、ラジカル重合性基を有する、＜１＞〜＜４＞のいずれか１つに記載のインプリント用硬化性組成物。
＜６＞ 上記式（１）のＲ^４またはＲ^５が下記式（１−３）で表される、＜１＞〜＜５＞のいずれか１つに記載のインプリント用硬化性組成物；

式（１−３）中、Ｒ^６は１価の有機基を表す；＊は結合位置を表す。
＜７＞ 上記式（１）のＲ^３および上記式（１−３）のＲ^６がそれぞれ独立に下記式（１−１）で表される、＜６＞に記載のインプリント用硬化性組成物；

式中、Ｒ^７は２価の有機基を表す；Ｒ^Ｃは水素原子またはメチル基を表す；＊は結合位置を表す。
＜８＞ 上記式（１）で表される化合物以外のラジカル重合性化合物の少なくとも１種が、下記式（２）で表される化合物を含む、＜１＞〜＜７＞のいずれか１つに記載のインプリント用硬化性組成物；

式（２）中、Ｒ^２１はｑ価の有機基であり、Ｒ^２２は水素原子またはメチル基であり、ｑは２以上の整数である。
＜９＞ 上記式（１）で表される化合物以外のラジカル重合性化合物の少なくとも１種が、単官能（メタ）アクリルモノマーである、＜１＞〜＜８＞のいずれか１つに記載のインプリント用硬化性組成物。
＜１０＞ 上記インプリント用硬化性組成物における溶剤の含有量が、５質量％以下である、＜１＞〜＜９＞のいずれか１つに記載のインプリント用硬化性組成物。
＜１１＞ 上記インプリント用硬化性組成物における重量平均分子量が２０００を超える成分の含有量が、５質量％以下である、＜１＞〜＜１０＞のいずれか１つに記載のインプリント用硬化性組成物。
＜１２＞ 上記インプリント用硬化性組成物の２５℃における粘度が３〜１５ｍＰａ・ｓである、＜１＞〜＜１１＞のいずれか１つに記載のインプリント用硬化性組成物。
＜１３＞ ＜１＞〜＜１２＞のいずれか１つに記載のインプリント用硬化性組成物から形成される硬化物。
＜１４＞ 上記硬化物が、シリコン基板の上に設けられている、＜１３＞に記載の硬化物。
＜１５＞ ＜１＞〜＜１２＞のいずれか１つに記載のインプリント用硬化性組成物を、基板上またはモールド上に適用し、上記インプリント用硬化性組成物を、上記モールドと上記基板で挟んだ状態で光照射することを含むパターン製造方法。
＜１６＞ 上記パターンのサイズが３０ｎｍ以下である、＜１５＞に記載のパターン製造方法。
＜１７＞ ＜１５＞または＜１６＞に記載のパターン製造方法で得られたパターンをマスクとしてエッチングを行う、被加工基板の製造方法。
＜１８＞ ＜１＞〜＜１２＞のいずれか１つに記載の硬化性組成物から形成されるパターンであって、パターンサイズが３０ｎｍ以下であるパターン。
＜１９＞ ＜１８＞に記載のパターンの少なくとも１種を含む、エッチング用マスク。
＜２０＞ 下記式（１）で表される化合物と下記式（２）で表される化合物とを含む、インプリント用重合性組成物；

式（１）中、Ｒ^１およびＲ^２は、それぞれ独立に、水素原子または炭素数１〜８の有機基であり、互いに結合して環を形成していてもよい；Ｒ^３は１価の有機基である；Ｒ^４およびＲ^５は、それぞれ独立に、水素原子または１価の有機基である；

式（２）中、Ｒ^２１はｑ価の有機基であり、Ｒ^２２は水素原子またはメチル基であり、ｑは２以上の整数である。 As a result of studies by the present inventor based on the above problems, it has been found that the above problems can be solved by blending a predetermined compound. Specifically, the above problems were solved by the following means <1>, preferably by <2> to <20>.
<1> A curable composition for imprint containing a compound represented by the following formula (1), a radically polymerizable compound other than the compound represented by the above formula (1), and a photoradical polymerization initiator;

In formula (1), R ¹ and R ² are independent hydrogen atoms or organic groups having 1 to 8 carbon atoms, and may be bonded to each other to form a ring; R ³ is monovalent. Organic groups; R ⁴ and R ⁵ are independently hydrogen atoms or monovalent organic groups.
<2> The content of the compound represented by the above formula (1) is 0.005 to 1 mass with respect to 100 parts by mass of the content of the radically polymerizable compound other than the compound represented by the above formula (1). The curable composition for imprint according to <1>, which is a part.
<3> The curable composition for imprint according to <1> or <2>, wherein the radically polymerizable compound other than the compound represented by the above formula (1) contains at least one (meth) acryloyl group. ..
<4> The curable composition for imprint according to any one of <1> to <3>, wherein the compound represented by the above formula (1) has a molecular weight of 100 to 1500.
<5> The curable composition for imprint according to any one of <1> to <4>, wherein the compound represented by the above formula (1) has a radically polymerizable group.
<6> The curable composition for imprint according to any one of <1> to <5>, wherein ^{R 4} or R ⁵ of the above formula (1) is represented by the following formula (1-3);

In formula (1-3), R ⁶ represents a monovalent organic group; * represents the bond position.
<7> The curable composition for imprint according to <6>, wherein ^{R 3} of the above formula (1) and R ^{6 of the above formula (1-3) are independently represented by the following formula (1-1).} Stuff;

In the formula, R ⁷ represents a divalent organic group; ^RC represents a hydrogen atom or a methyl group; * represents a bond position.
<8> Any one of <1> to <7>, wherein at least one of the radically polymerizable compounds other than the compound represented by the above formula (1) contains a compound represented by the following formula (2). The curable composition for imprint described in the above;

In formula (2), R ²¹ is a q-valent organic group, R ²² is a hydrogen atom or a methyl group, and q is an integer of 2 or more.
<9> The description of any one of <1> to <8>, wherein at least one of the radically polymerizable compounds other than the compound represented by the above formula (1) is a monofunctional (meth) acrylic monomer. Curable composition for imprint.
<10> The curable composition for imprint according to any one of <1> to <9>, wherein the content of the solvent in the curable composition for imprint is 5% by mass or less.
<11> The imprint according to any one of <1> to <10>, wherein the content of the component having a weight average molecular weight of more than 2000 in the curable composition for imprint is 5% by mass or less. Curable composition.
<12> The curable composition for imprint according to any one of <1> to <11>, wherein the curable composition for imprint has a viscosity of 3 to 15 mPa · s at 25 ° C.
<13> A cured product formed from the curable composition for imprint according to any one of <1> to <12>.
<14> The cured product according to <13>, wherein the cured product is provided on a silicon substrate.
<15> The curable composition for imprint according to any one of <1> to <12> is applied onto a substrate or a mold, and the curable composition for imprint is applied to the mold and the mold. A pattern manufacturing method including irradiating light while sandwiched between substrates.
<16> The pattern manufacturing method according to <15>, wherein the size of the pattern is 30 nm or less.
<17> A method for manufacturing a substrate to be processed, wherein etching is performed using the pattern obtained by the pattern manufacturing method according to <15> or <16> as a mask.
<18> A pattern formed from the curable composition according to any one of <1> to <12>, wherein the pattern size is 30 nm or less.
<19> An etching mask containing at least one of the patterns described in <18>.
<20> A polymerizable composition for imprint containing a compound represented by the following formula (1) and a compound represented by the following formula (2);

In formula (1), R ¹ and R ² are independent hydrogen atoms or organic groups having 1 to 8 carbon atoms, and may be bonded to each other to form a ring; R ³ is monovalent. Organic groups; R ⁴ and R ⁵ are independently hydrogen atoms or monovalent organic groups;

In formula (2), R ²¹ is a q-valent organic group, R ²² is a hydrogen atom or a methyl group, and q is an integer of 2 or more.

According to the present invention, a curable composition for imprint, a cured product, a pattern manufacturing method, a lithography method, a pattern, a mask for lithography, and a curable composition for imprint, which has high adhesion to a substrate when made into a cured product and has excellent storage stability. It has become possible to provide a polymerizable composition for imprinting.

Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the present specification, "(meth) acrylate" represents acrylate and methacrylate, "(meth) acrylic" represents acrylic and methacrylic, and "(meth) acryloyl" represents acryloyl and methacryloyl. "(Meta) acryloyloxy" stands for acryloyloxy and methacryloyloxy.
As used herein, "imprint" preferably refers to a pattern transfer having a size of 1 nm to 10 mm, and more preferably a pattern transfer having a size of about 10 nm to 100 μm (nanoimprint).
In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "light" includes not only light having wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared regions, and electromagnetic waves, but also radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. As these lights, monochrome light (single wavelength light) that has passed through an optical filter may be used, or light having a plurality of different wavelengths (composite light) may be used.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent.
Unless otherwise specified, the atmospheric pressure at the time of boiling point measurement in the present invention is 101325 Pa (1 atmospheric pressure). Unless otherwise specified, the temperature in the present invention is 25 ° C.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000 or TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the eluate shall be measured using THF (tetrahydrofuran). Unless otherwise specified, a detector having a wavelength of 254 nm for UV rays (ultraviolet rays) is used for detection.

The curable composition for imprint of the present invention comprises a compound represented by the following formula (1) and a radically polymerizable compound other than the compound represented by the formula (1) (hereinafter, simply "other radically polymerizable compounds". It may be referred to as "compound" or "polymerizable compound without aminomethyl group") and a photoradical polymerization initiator.

式（１）中、Ｒ^１およびＲ^２は、それぞれ独立に、水素原子または炭素数１〜８の有機基であり、互いに結合して環を形成していてもよい；Ｒ^３は１価の有機基であり；Ｒ^４およびＲ^５は、それぞれ独立に、水素原子または１価の有機基である。

In formula (1), R ¹ and R ² are independent hydrogen atoms or organic groups having 1 to 8 carbon atoms, and may be bonded to each other to form a ring; R ³ is monovalent. It is an organic group; R ⁴ and R ⁵ are independently hydrogen atoms or monovalent organic groups.

With such a configuration, it is possible to provide a curable composition for imprinting, which is excellent in adhesion to a substrate when made into a cured product and storage stability of the composition before curing. Further, preferably, it becomes possible to provide a curable composition for imprint having excellent mold releasability.
In this mechanism, the amino group (R ¹ R ² N-) (the <ii> portion of the following formula) acts to enhance the adhesion to the substrate, and the methylene group (-CH _2- ) (<i> of the following formula). It is presumed that the radicals generated in (part>) act to trap the reactive oxygen species in the system that destabilize the composition (see formula 1a below).

以下、本発明について、詳細に説明する。

Hereinafter, the present invention will be described in detail.

<Compound represented by formula (1)>
The curable composition for imprinting of the present invention contains the compound represented by the above formula (1). The compound represented by the formula (1) preferably has a radically polymerizable group. By having a radically polymerizable group, it becomes a part of the cured product, and the adhesion to the resist tends to be further improved. Preferred radically polymerizable groups are the same as those specified in later R ^3. The number of radically polymerizable groups is preferably 1 to 5, more preferably 2 to 5, and further preferably 2 or 3 in one molecule of the compound represented by the formula (1). Preferably, the number is more preferably two.

In the formula (1), R ¹ and R ² are independently hydrogen atoms or organic groups having 1 to 8 carbon atoms, preferably hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and hydrogen atoms. , Methyl group, ethyl group, n-propyl group, isopropyl group, benzyl group are more preferable, hydrogen atom, methyl group or ethyl group is more preferable, methyl group or ethyl group is more preferable, and ethyl group is even more preferable. R ¹ and R ² may or may not have the following substituent T as long as the effects of the present invention are not impaired. In the present invention, it is preferable that R ¹ and R ² do not have a substituent. If it has a substituent, an aryl group is preferable.
One embodiment of the present invention is that R ¹ and R ² are the same group. With such a configuration, the effect of the present invention is more effectively exhibited.

As the substituent T, a linear or branched alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms), a cycloalkyl group (preferably 3 to 24 carbon atoms, 3). ~ 12 is more preferred, 3-6 is more preferred), aralkyl groups (7-21 carbon atoms are preferred, 7-15 are more preferred, 7-11 are even more preferred), linear or branched alkenyl groups (carbon number). 2 to 24 are preferred, 2 to 12 are more preferred, 2 to 6 are even more preferred), cycloalkenyl groups (3 to 24 carbon atoms are preferred, 3 to 12 are more preferred, 3 to 6 are even more preferred), hydroxyls. Group, hydroxylalkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12; even more preferably 1 to 6; the number of hydroxyl groups is preferably 1 to 6, more preferably 1 to 3, the alkyl group is direct. It may be chain or branched, chain or cyclic), hydroxylalkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12 and even more preferably 2 to 6; preferably 1 to 6 hydroxyl groups. , 1-3 are more preferred, the alkenyl group may be linear or branched, chain or cyclic), amino group (preferably 0 to 24 carbon atoms, more preferably 0 to 12 and even more preferably 0 to 6). ), Aminoalkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12; still more preferably 1 to 6; the number of amino groups is preferably 1 to 6, more preferably 1 to 3, the alkyl group is direct. It may be chain or branched, chain or cyclic), aminoalkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12 and even more preferably 2 to 6; preferably 1 to 6 amino groups. , 1-3 are more preferred, the alkenyl group may be linear or branched, chain or cyclic), thiol group, thiolalkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 and 1 to 1). 6 is more preferred; the number of thiol groups is preferably 1-6, more preferably 1-3, alkyl groups may be linear or branched, chain or cyclic), thiolalkenyl groups (2 to 24 carbon atoms). 2-12 is more preferred, 2-6 is even more preferred; the number of thiol groups is preferably 1-6, more preferably 1-3, the alkenyl group may be linear or branched, chained or cyclic. Good), carboxyl group, carboxyalkyl group (1 to 24 carbon atoms are preferable, 1 to 12 are more preferable, and 1 to 6 are even more preferable. The number of carboxyl groups is preferably 1 to 6, more preferably 1-3, alkyl groups may be linear or branched, chain or cyclic), carboxyalkenyl groups (preferably 2 to 24 carbon atoms). 2 to 12 are more preferable, 2 to 6 are more preferable; the number of carboxyl groups is preferably 1 to 6, 1 to 3 is more preferable, and the alkenyl group may be linear or branched, and may be chain or cyclic). Acryloyl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10), acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms). ), Acryloyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), acryloyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, 7 to 11 carbon atoms). More preferably), acryloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11), heterocyclic group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms). , 2-5 are more preferably containing a 5-membered ring or a 6-membered ring), (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloyloxyalkyl group (alkyl group has 1 to 1 carbon atoms). 24 is preferred, 1-12 is more preferred, 1-6 is even more preferred; the alkyl group may be linear or branched, chain or cyclic), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.). iodine), oxo (= O), imino (= ^NR N), an alkylidene group _{^{(= C (R N) 2}} ) , and the like. ^RN represents a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, still more preferably a methyl group).

R ³ is a monovalent organic group, preferably an organic group having 1 to 40 carbon atoms, more preferably an organic group having 2 to 30 carbon atoms, and an organic group having 3 to 20 carbon atoms. It is more preferable to have 6 to 20 carbon atoms. R ³ preferably contains one or two (preferably one) radical-polymerizable groups and preferably has the same radical-polymerizable groups as the radical-polymerizable groups of other radical-polymerizable compounds. R ³ is more preferably an organic group contained in other radically polymerizable compounds. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinylphenyl group, a vinyl group, a (meth) acryloyl group and an allyl group, and a (meth) acryloyl group is preferable, and an acryloyl group is more preferable. By using the (meth) acryloyl group, the adhesion between the substrate and the curable composition for imprinting tends to be further improved.

式中、Ｒ^７は２価の有機基を表す；Ｒ^Ｃは水素原子またはメチル基を表す；＊は結合位置を表す。
このような構成とすることにより、基板とインプリント用硬化性組成物の密着性がより向上する傾向にある。 R ³ is preferably represented by the following formula (1-1).

In the formula, R ⁷ represents a divalent organic group; ^RC represents a hydrogen atom or a methyl group; * represents a bond position.
With such a configuration, the adhesion between the substrate and the curable composition for imprinting tends to be further improved.

式中、Ｚ^１およびＺ^２はそれぞれ独立に、単結合、−Ａｌｋ−、または−ＡｌｋＯ−であることが好ましい。Ａｌｋはアルキレン基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３がさらに好ましい）を表し、本発明の効果を損ねない範囲で、置換基Ｔを有していてもよい。この置換基の好ましい例としては、下記Ｒ^１０１〜Ｒ^１１７と同義の基が挙げられる。なお、−ＡｌｋＯ−のＯ（酸素原子）はＲ^９側になるように連結する。 The ^RC is preferably a hydrogen atom.
The organic group of R ⁷ is preferably a linking group represented by the following formula (1-2).

In the formula, Z ¹ and Z ² are preferably single bonds, -Alk-, or -ArkO-, respectively. Alk represents an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and may have a substituent T as long as the effects of the present invention are not impaired. .. Preferred examples of this substituent include groups synonymous with the following ^{R 101 to} R ^117. Incidentally, O (oxygen atom) of -AlkO- is coupled so that the ^{R 9} side.

R ⁹ is preferably a single bond or a linking group selected from the following formulas (9-1) to (9-10) or a combination thereof. Of these, a linking group selected from the formulas (9-1) to (9-3), (9-7), and (9-8) is preferable.

R ^{101 to} R ¹¹⁷ are arbitrary substituents, and the substituent T is preferable. Among them, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and an acryloyl group (preferably 7 to 21 carbon atoms, 7 to 15 carbon atoms are more preferable, 7 to 11 carbon atoms are preferable). (More preferably), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10), thienyl group, frill group, (meth) acryloyl group, (meth) acryloyloxy group, ( Meta) Acryloyloxyalkyl groups (alkyl groups preferably have 1 to 24 carbon atoms, more preferably 1 to 12 and even more preferably 1 to 6) are preferred. R ¹⁰¹ and R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ , R ¹⁰⁵ and R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹⁰ , R ¹¹¹ when there are multiple, R ¹¹² when there are multiple, R ^{113 when there are multiple.} , R ¹¹⁴ when there are a plurality of them, R ¹¹⁵ when there are a plurality of them, R ¹¹⁶ when there are a plurality of them, and R ¹¹⁷ when there are a plurality of them may be combined with each other to form a ring. Examples of the linking group L when the ring is formed include an example of the linking group L described later, and among them, an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) is preferable. For example, the cyclohexane rings of formulas (9-6) and (9-7) may form a norbornane ring or an adamantane ring. R ^{101 to} R ¹¹⁷ may further have a substituent T as long as the effects of the present invention are not impaired.
Further, when R ⁹ has a ring structure, it is a structure containing an alicyclic or an aromatic ring described later in "(3) Alicyclic or aromatic ring substituted with a linear or branched alkyl group having 5 or more carbon atoms". It is also preferable.
As the linking group L, a linear or branched alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms), a linear or branched alkenylene group (carbon number 2). 24, more preferably 2 to 12, more preferably 2 to 6), - O -, - S -, - CO -, - NR N -, - NR N CO-, and connected according to a combination thereof The group is mentioned. ^RN is synonymous with the above. The number of atoms contained in the linking group L is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6.
p is an integer of 0 or more and not more than the maximum number that can be substituted for each ring. In each case, the upper limit value is preferably half or less of the maximum number of substitutables, more preferably 4 or less, and further preferably 2 or less.
* Represents the bond position.
Ar is an arylene group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and specifically, a phenylene group, a naphthalene diyl group, an anthracene diyl group, a phenanthrene diyl group, Examples include the full orange yl group.
Examples of Z ³ include a single bond or a linking group L. Among Z ³ , a single bond, —O—, or an alkylene group (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, particularly preferably a methylene group and a 2,2-propylene diyl group) is preferable. When Z ³ is an alkylene group, the substituent T may be substituted, and in particular, a halogen atom (particularly a fluorine atom) may be substituted.
hCy is a heterocyclic group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 2 to 5 carbon atoms), and a 5-membered ring or a 6-membered ring is more preferable. Specific examples of the heterocycles constituting hCy include thiophene ring, furan ring, dibenzofuran ring, carbazole ring, indole ring, tetrahydropyran ring, tetrahydrofuran ring, pyrrole ring, pyridine ring, pyrazole tube, imidazole ring, benzimidazole ring, and the like. Examples thereof include a triazole ring, a thiazole ring, an oxazole ring, a pyrrolidone ring and a morpholin ring, and among them, a thiophene ring, a furan ring and a dibenzofuran ring are preferable.
n and m are natural numbers of 100 or less, preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

In formula (1), R ⁴ and R ⁵ are independently hydrogen atoms or monovalent organic groups. The monovalent organic group is preferably an organic group having 1 to 40 carbon atoms, more preferably an organic group having 3 to 35 carbon atoms, and further preferably an organic group having 5 to 30 carbon atoms. Preferably, it may have 8 to 20 carbon atoms. R ⁴ and R ⁵ preferably contain a radically polymerizable group, and may have the same radically polymerizable group as the radically polymerizable group of a radically polymerizable compound other than the compound represented by the formula (1) described later. preferable. At ^{least one of R 4} and R ⁵ preferably contains the organic group ^{of R 3} in the formula (1). Further, ^{it is more preferable that at least one of R 4} and R ⁵ has the same organic group as that of other radically polymerizable compounds. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinylphenyl group, a vinyl group, a (meth) acryloyl group and an allyl group. The radically polymerizable group is preferably a (meth) acryloyl group.

R ⁴ or R ⁵ of the formula (1) is an organic group represented by (i) both of which are hydrogen atoms, or (ii) one of which is a hydrogen atom and the other of which is represented by the following formula (1-3). One embodiment is preferable, and (ii) one is a hydrogen atom and the other is an organic group represented by the following formula (1-3). The effect of the present invention can be more effectively exhibited by using the organic group represented by the formula (1-3).

式中、Ｒ^６は１価の有機基を表し、上記Ｒ^３と同義の基であることが好ましい。その好ましい範囲もＲ^３と同じである。＊は結合位置を表す。

In the formula, R ⁶ represents a monovalent organic group, and is preferably a group synonymous with ^{R 3 above.} And a preferred range is also the same as R ^3. * Represents the bond position.

式中、Ｒ^７は２価の有機基を表す；Ｒ^８はアルキル基を表す。
Ｒ^７の好ましい範囲は、式（１−１）におけると同義であり、好ましい範囲も同様である。
Ｒ^８は本発明の効果を損ねない範囲で、置換基Ｔを有していてもよい。この置換基としては、例えば、アミノ基（炭素数０〜１２が好ましく、０〜６がより好ましく、０〜３がさらに好ましい）が挙げられる。 Other preferred embodiments of R ^3, is also exemplified groups represented by the following formula.

In the formula, R ⁷ represents a divalent organic group; R ⁸ represents an alkyl group.
The preferable range of R ⁷ is synonymous with that in the formula (1-1), and the preferable range is also the same.
R ⁸ may have a substituent T as long as the effect of the present invention is not impaired. Examples of the substituent include an amino group (preferably 0 to 12 carbon atoms, more preferably 0 to 6 carbon atoms, still more preferably 0 to 3 carbon atoms).

式（１−４）中、Ｒ^１〜Ｒ^３は、それぞれ独立に、式（１）におけるＲ^１〜Ｒ^３と同義であり、好ましい範囲も同様である。式（１−４）において、２つのＲ^３は同一であっても異なっていてもよいが、同一であることが好ましい。 The compound represented by the formula (1) is more preferably represented by the following formula (1-4).

In the formula (1-4), R ^{1 to} R ^{3 are independently synonymous with R 1 to} R ³ in the formula (1), and the preferable range is also the same. In the formula (1-4), the two R ³ may be the same or different, but are preferably the same.

The compound represented by the above formula (1) preferably has a molecular weight of 100 to 1500, more preferably 150 to 1300, further preferably 200 to 1000, and even 200 to 700. Good. Within such a range, the effect of improving the adhesion by adding a small amount can be more effectively exhibited.
The compound represented by the above formula (1) does not have to have a radically polymerizable group, but preferably has a radically polymerizable group, and at least one of ^{R 3 to} R ^{5 is radically polymerizable.} It is more preferable to have a group, and it is further preferable that one of R ³ and R ⁴ and R ⁵ has a radically polymerizable group.
The ^{two selected from R 3 to} R ⁵ may be bonded to each other to form a ring. Any linking group may intervene in the formed ring, and examples thereof include a linking group L.
The compound represented by the formula (1) is preferably composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and nitrogen atoms.

Specific examples of the compound represented by the formula (1) include the following compounds.

The content of the compound represented by the above formula (1) in the curable composition for imprint of the present invention is based on 100 parts by mass of the content of the radically polymerizable compound other than the compound represented by the formula (1). , 0.005 to 1 part by mass, more preferably 0.01 to 0.75 part by mass, and even more preferably 0.05 to 0.5 part by mass. Within such a range, the adhesion, the mold release force, and the stability over time tend to be well-balanced and more excellent.
In the curable composition for imprinting of the present invention, the compound represented by the above formula (1) and the compound represented by the formula (2) described later may be combined with other components as necessary to carry out polymerization for imprinting. It may constitute a sex composition. The content of the compound represented by the above formula (1) in the curable composition for imprint of the present invention is 0.005 with respect to 100 parts by mass of the content of the compound represented by the formula (2) described later. It is preferably ~ 1 part by mass, more preferably 0.01 to 0.75 part by mass, and further preferably 0.05 to 0.5 part by mass. Within such a range, the adhesion, the mold release force, and the stability over time tend to be well-balanced and more excellent.
Further, in the curable composition for imprint of the present invention, the compound represented by the formula (1) is preferably 0.005 to 1% by mass of the total solid content of the curable composition for imprint. It is more preferably 0.01 to 0.75% by mass, and even more preferably 0.05 to 0.5% by mass.
By setting the above content (the amount of the compound of the formula (1) to be blended) to the above upper limit or less, good releasability can be maintained, which is preferable. On the other hand, by setting this content to the above lower limit value or more, the above-mentioned adhesion and stability are more effectively exhibited, which is preferable.
In the curable composition for imprint of the present invention, the compound represented by the above formula (1) may contain only one kind or two or more kinds. When two or more types are included, the total amount is preferably in the above range.

<Radical polymerizable compounds other than the compound represented by the formula (1)>
The curable composition for imprint of the present invention contains a radically polymerizable compound (another radically polymerizable compound) other than the compound represented by the formula (1). Other radically polymerizable compounds preferably do not have an aminomethyl group.
The other radically polymerizable compound may be a monofunctional radically polymerizable compound having one radically polymerizable group or a polyfunctional radically polymerizable compound having two or more radically polymerizable groups. The curable composition for imprint of the present invention preferably contains a polyfunctional radical-polymerizable compound, and more preferably contains both a polyfunctional radical-polymerizable compound and a monofunctional radical-polymerizable compound.
The polyfunctional radical-polymerizable compound preferably contains at least one of a bifunctional radical-polymerizable compound and a trifunctional radical-polymerizable compound, and more preferably contains at least one of a bifunctional radical-polymerizable compound.

Examples of the radically polymerizable group contained in the other radically polymerizable compound include a group having an ethylenically unsaturated bond such as a vinylphenyl group, a vinyl group, a (meth) acryloyl group and an allyl group. The radically polymerizable group is preferably a (meth) acryloyl group, more preferably an acryloyl group.

The content of the other radically polymerizable compound in the curable composition for imprint of the present invention is preferably 40 to 99.9% by mass, more preferably 60 to 99% by mass, and 75 to 98% by mass. It is more preferably mass%.
The other radically polymerizable compound may contain only one kind, or may contain two or more kinds. When two or more types are contained, the total amount is preferably in the above range.

<< Polyfunctional Radical Polymerizable Compound >>
In the present invention, it is preferable that the radically polymerizable compound other than the compound represented by the above formula (1) contains a compound represented by the following formula (2). Within such a range, the adhesion, the mold release force, and the stability over time tend to be well-balanced and more excellent.

In the formula, R ²¹ is a q-valent organic group, R ²² is a hydrogen atom or a methyl group, and q is an integer of 2 or more. q is preferably an integer of 2 or more and 7 or less, more preferably an integer of 2 or more and 4 or less, further preferably 2 or 3, and even more preferably 2.
R ²¹ is preferably a 2- to 7-valent organic group, more preferably a 2- to 4-valent organic group, further preferably a divalent or trivalent organic group, and a divalent organic group. Is more preferable. R ²¹ is preferably a hydrocarbon group having at least one linear, branched and cyclic structure. The hydrocarbon group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.
When R ²¹ is a divalent organic group, it is preferably a linking group represented by the above formula (1-2), and the preferred range thereof is also the same. It is mentioned as a preferable aspect of the present invention that the structure of the formula (1-2) in the formula (1) and the structure of the formula (1-2) in the formula (2) match in the composition.
When R ²¹ has a ring structure, it may also have a structure containing an alicyclic or an aromatic ring described in "(3) Alicyclic or aromatic ring substituted with a linear or branched alkyl group having 5 or more carbon atoms". It is also preferable.

式（２−１）中、Ｒ^７およびＲ^Ｃは上記式（１−１）で規定したものと同義である。 The polyfunctional radical polymerizable compound is preferably represented by the following formula (2-1).

In the formula (2-1), R ⁷ and ^RC are synonymous with those specified in the above formula (1-1).

These polyfunctional radical polymerizable compounds may contain only one kind or two or more kinds.
The polyfunctional radically polymerizable compound used in the present invention preferably has an Onishi parameter described later of 4.5 or less. The lower limit of the Onishi parameter is not specified, but may be, for example, 2.0 or more.
The molecular weight of the polyfunctional radically polymerizable compound used in the present invention is preferably 1000 or less, more preferably 800 or less, further preferably 500 or less, further preferably 350 or less, and even more preferably 230 or less. By setting the upper limit of the molecular weight to be equal to or lower than the above upper limit, the viscosity of the compound tends to be reduced.
The lower limit of the molecular weight is not particularly specified, but can be, for example, 170 or more.

The number of polymerizable groups contained in the polyfunctional radical polymerizable compound used in the present invention is 2 or more, preferably 2 to 7, more preferably 2 to 4, further preferably 2 or 3, and even more preferably 2.

The type of atom constituting the polyfunctional radical polymerizable compound used in the present invention is not particularly specified, but it is preferably composed of only an atom selected from a carbon atom, an oxygen atom, a hydrogen atom and a halogen atom, and carbon. More preferably, it is composed only of atoms selected from atoms, oxygen atoms and hydrogen atoms.

The polyfunctional radical polymerizable compound used in the present invention preferably has a viscosity at 25 ° C. of 180 mPa · s or less, more preferably 10 mPa · s or less, further preferably 7 mPa · s or less, and further preferably 5 mPa · s or less. preferable. The lower limit of the viscosity is not particularly specified, but can be, for example, 2 mPa · s or more.

Examples of the polyfunctional radical polymerizable compound preferably used in the present invention include the polymerizable compounds described in JP-A-2014-170949, the contents of which are included in the present specification.
Specific examples of the compound represented by the formula (2) include the following compounds.

The amount of the polyfunctional radically polymerizable compound used in the present invention with respect to the total radically polymerizable compound in the curable composition for imprint is preferably 30 to 99% by mass, preferably 50 to 95% by mass. Is more preferable, and is further preferably 75 to 90% by mass, and may be 80 to 90% by mass.
The polyfunctional radical polymerizable compound may contain only one kind, or may contain two or more kinds. When two or more types are contained, the total amount is preferably in the above range.
The method for producing the polyfunctional radically polymerizable compound may be a conventional method. Some synthetic methods or sources are listed for some exemplary compounds. B-22 can be synthesized from α, α'-dichloro-m-xylene and acrylic acid. B-16 can be synthesized from 1,4-cyclohexanedimethanol and acryloyl chloride. As B-14, A-DCP (trade name) manufactured by Shin Nakamura Chemical Industry Co., Ltd. can be used. As B-32, Kyoeisha Chemical Co., Ltd. Light Acrylate BP-4PA (trade name) can be used. B-9 can use A-NPG (trade name) manufactured by Shin Nakamura Chemical Industry Co., Ltd., and B-3 can use A-HD-N (trade name) manufactured by Shin Nakamura Chemical Industry Co., Ltd. For B-6, Kyoeisha Chemical Co., Ltd. Light Ester 2EG (trade name) can be used. B-2 can be synthesized from cis-2-butene-1,4-diol and acryloyl chloride. For B-10, SR341 (trade name) manufactured by Sartmer can be used.

<< Monofunctional Radical Polymerizable Compound >>
The type of the monofunctional radically polymerizable compound used in the present invention is not particularly defined as long as it does not deviate from the gist of the present invention. The monofunctional radically polymerizable compound used in the present invention preferably has a linear or branched hydrocarbon chain having 4 or more carbon atoms. In the present invention, only one type of monofunctional radically polymerizable compound may be contained, or two or more types may be contained.

The monofunctional radical polymerizable compound used in the present invention preferably has an Onishi parameter of 8.1 or less, more preferably 4.0 or less, and even more preferably 3.9 or less. It is more preferably 7 or less, and even more preferably 3.5 or less. The lower limit of the Onishi parameter is not particularly specified, but can be, for example, 2.0 or more, and further 2.5 or more. When the Onishi parameter is 4.0 or less, the etching rate can be lowered, the etching selection ratio with the processing target is improved, and the etching processing margin is expanded.
Here, the Onishi parameter is a value calculated by the following formula.
Onishi parameter = (sum of atomic numbers of C, H, and O) / (number of C atoms-O atomic number)
The molecular weight of the monofunctional radically polymerizable compound used in the present invention is preferably 50 or more, more preferably 150 or more, and even more preferably 220 or more. The upper limit of the molecular weight is preferably 1000 or less, more preferably 800 or less, further preferably 300 or less, and even more preferably 270 or less. By setting the molecular weight to the above lower limit value or more, the volatility tends to be suppressed. By setting the molecular weight to the above upper limit or less, the viscosity tends to be reduced.
The boiling point of the monofunctional radically polymerizable compound used in the present invention at 1013 hPa is not particularly specified, and may be, for example, less than 60 ° C. or 60 ° C. or higher. One embodiment of the boiling point is 80 ° C. or higher. Volatility can be suppressed by setting the boiling point at 667 Pa to be equal to or higher than the above lower limit. The upper limit of the boiling point is not particularly specified, but for example, the boiling point at 667 Pa can be 170 ° C. or lower.

The monofunctional radically polymerizable compound used in the present invention is preferably liquid at 25 ° C.
In the present invention, the liquid at 25 ° C. means a compound having fluidity at 25 ° C., for example, a compound having a viscosity at 25 ° C. of 1 to 100,000 mPa · s. The viscosity of the monofunctional radically polymerizable compound at 25 ° C. is, for example, more preferably 10 to 20,000 mPa · s, and even more preferably 100 to 15,000 mPa · s.
By using a compound that is liquid at 25 ° C., a solvent-free structure can be obtained. Here, the term "substantially free of solvent" means, for example, that the content of the solvent in the curable composition for imprinting of the present invention is 5% by mass or less, and further, 3% by mass or less. In particular, it means that it is 1% by mass or less.
The viscosity of the monofunctional radically polymerizable compound used in the present invention at 25 ° C. is preferably 100 mPa · s or less, more preferably 10 mPa · s or less, further preferably 8 mPa · s or less, still more preferably 6 mPa · s or less. By setting the viscosity of the monofunctional radical polymerizable compound at 25 ° C. or less to the above upper limit value or less, the viscosity of the curable composition for imprinting can be reduced, and the filling property tends to be improved. The lower limit value is not particularly specified, but may be, for example, 1 mPa · s or more.

The monofunctional radically polymerizable compound used in the present invention is preferably a monofunctional (meth) acrylic monomer, and more preferably a monofunctional acrylate.

The type of atom constituting the monofunctional radical polymerizable compound used in the present invention is not particularly specified, but it is preferably composed of only an atom selected from a carbon atom, an oxygen atom, a hydrogen atom and a halogen atom, and carbon. More preferably, it is composed only of atoms selected from atoms, oxygen atoms and hydrogen atoms.

The monofunctional radically polymerizable compound used in the present invention preferably has a linear or branched hydrocarbon chain having 4 or more carbon atoms. The hydrocarbon chain in the present invention represents an alkyl chain, an alkenyl chain, or an alkynyl chain, and an alkyl chain or an alkenyl chain is preferable, and an alkyl chain is more preferable.
In the present invention, the alkyl chain represents an alkyl group and an alkylene group. Similarly, the alkenyl chain represents an alkenyl group and an alkenylene group, and the alkynyl chain represents an alkynyl group and an alkynylene group. Among these, a linear or branched alkyl group or alkenyl group is more preferable, a linear or branched alkyl group is further preferable, and a linear alkyl group is further preferable.
The linear or branched hydrocarbon chain (preferably an alkyl group) has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more carbon atoms, further preferably 10 or more carbon atoms, and further preferably 10 or more carbon atoms. 12 or more is more preferable. The upper limit of the number of carbon atoms is not particularly specified, but may be, for example, 25 or less carbon atoms.
The straight-chain or branched hydrocarbon chain may contain an ether group (-O-), but it is preferable that the straight-chain or branched hydrocarbon chain does not contain an ether group from the viewpoint of improving releasability.
By using a monofunctional radically polymerizable compound having such a hydrocarbon chain, the elastic modulus of the cured film is reduced and the releasability is improved with a relatively small amount of addition. Further, when a monofunctional radical polymerizable compound having a linear or branched alkyl group is used, the interfacial energy between the mold and the cured film can be reduced, and the releasability can be further improved.
Preferred hydrocarbon groups of the monofunctional radically polymerizable compound used in the present invention include (1) to (3).
(1) Linear alkyl group having 8 or more carbon atoms (2) Branched alkyl group having 10 or more carbon atoms (3) Alicyclic or aromatic ring substituted with a linear or branched alkyl group having 5 or more carbon atoms

<<< (1) Linear alkyl group with 8 or more carbon atoms >>>
The linear alkyl group having 8 or more carbon atoms is more preferably 10 or more carbon atoms, further preferably 11 or more carbon atoms, and further preferably 12 or more carbon atoms. Further, the carbon number of 20 or less is preferable, the carbon number of 18 or less is more preferable, the carbon number of 16 or less is further preferable, and the carbon number of 14 or less is further preferable.
<<< (2) Branched alkyl group with 10 or more carbon atoms >>>
The branched alkyl group having 10 or more carbon atoms preferably has 10 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, further preferably 10 to 14 carbon atoms, and even more preferably 10 to 12 carbon atoms.
<<< (3) Alicyclic or aromatic ring substituted with a linear or branched alkyl group having 5 or more carbon atoms >>>
The linear or branched alkyl group having 5 or more carbon atoms is more preferably a linear alkyl group. The number of carbon atoms of the alkyl group is more preferably 6 or more, further preferably 7 or more, and even more preferably 8 or more. The number of carbon atoms of the alkyl group is preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less.
The ring structure of the alicyclic or aromatic ring may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. In the case of condensed rings, the number of rings is preferably two or three. The ring structure is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. The ring structure is an alicyclic ring or an aromatic ring, but an aromatic ring is preferable. Specific examples of the ring structure include a cyclohexane ring, a norbornane ring, an isobornane ring, a tricyclodecane ring, a tetracyclododecane ring, an adamantane ring, a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. , Tricyclodecane ring, adamantane ring, benzene ring are more preferable, and benzene ring is further preferable.

The monofunctional radical polymerizable compound used in the present invention is preferably a compound in which a linear or branched hydrocarbon chain having 4 or more carbon atoms and a polymerizable group are directly bonded or via a linking group, as described above (1). ) To (3), a compound in which a polymerizable group is directly bonded to any one of the groups is more preferable. Examples of the linking group include -O-, -C (= O)-, -CH _2- or a combination thereof. Examples of the monofunctional radically polymerizable compound used in the present invention include (1) a linear alkyl (meth) acrylate in which a linear alkyl group having 8 or more carbon atoms and a (meth) acryloyloxy group are directly bonded. Especially preferable.
Examples of the monofunctional radically polymerizable compound preferably used in the present invention include the following first and second groups and the compounds used in other examples. However, it goes without saying that the present invention is not limited thereto. Also, the first group is more preferable than the second group.
Group 1

Group 2

The lower limit of the amount of the monofunctional radically polymerizable compound used in the present invention with respect to the total radically polymerizable compound in the curable composition for imprint is preferably 1% by mass or more, more preferably 3% by mass or more. 5% by mass or more is more preferable, and 7% by mass or more is further preferable. The upper limit is more preferably 29% by mass or less, more preferably 27% by mass or less, particularly preferably 25% by mass or less, further preferably 20% by mass or less, and even more preferably 15% by mass or less. By setting the amount of the monofunctional radically polymerizable compound to the above lower limit value or more with respect to the total radically polymerizable compound, the releasability can be improved, and defects and mold breakage can be suppressed at the time of mold releasation. Further, when the value is not more than the above upper limit value, the Tg of the cured film of the curable composition for imprinting can be increased, and the etching processability, particularly the waviness of the pattern at the time of etching can be suppressed.

In the present invention, a monofunctional radically polymerizable compound other than the above monofunctional radically polymerizable compound may be used as long as the gist of the present invention is not deviated, and among the polymerizable compounds described in JP-A-2014-170949, among the polymerizable compounds described in JP-A-2014-170949, Monofunctional radically polymerizable compounds are exemplified, and their contents are included in the present specification.
In the present invention, 90% by mass or more of the total monofunctional radically polymerizable compound contained in the curable composition for imprint is a monofunctional radically polymerizable compound having the groups (1) to (3) above. It is preferably 95% by mass or more, and more preferably 95% by mass or more.

<Photoradical polymerization initiator>
The curable composition for imprint of the present invention contains a photoradical polymerization initiator.
As the photoradical polymerization initiator used in the present invention, any compound that generates an active species that polymerizes the above-mentioned radically polymerizable compound by light irradiation can be used.

As the photoradical polymerization initiator, for example, a commercially available initiator can be used. As these examples, for example, those described in paragraph No. 0091 of JP-A-2008-105414 can be preferably adopted. Of these, acetophenone-based compounds, acylphosphine oxide-based compounds, and oxime ester-based compounds are preferable from the viewpoint of curing sensitivity and absorption characteristics. Commercially available products include Irgacure® 1173, Irgacure 184, Irgacure 2959, Irgacure 127, Irgacure 907, Irgacure 369, Irgacure 379, Lucyrin® TPO, Irgacure 819, Irgacure OXE-01, Irgacure OXE-02. Examples thereof include Irgacure 651 and Irgacure 754 (all manufactured by BASF).
In the present invention, an oxime compound having a fluorine atom can also be used as the photoradical polymerization initiator. Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like. These contents are incorporated in the present specification.

The photoradical polymerization initiator may be used alone, but it is also preferable to use two or more in combination. Specifically, combinations of Irgacure 1173 and Irgacure 907, Irgacure 1173 and Lucyrin TPO, Irgacure 1173 and Irgacure 819, Irgacure 1173 and Irgacure OXE01, Irgacure 907 and Lucirin TPO, and Irgacure 907 and Irgacure 819 are exemplified. With such a combination, the exposure margin can be expanded.

The imprintable curable composition used in the present invention preferably contains 0.01 to 10% by mass of a photoradical polymerization initiator, more preferably 0.1 to 5% by mass, and even more preferably 0. .5 to 3% by mass. The curable composition for imprint may contain only one type of photoradical polymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<Sensitizer>
In addition to the photoradical polymerization initiator, a sensitizer may be added to the curable composition for imprint used in the present invention. When the curable composition for imprint of the present invention is difficult to cure in an oxygen atmosphere, the curability can be improved by adding a sensitizer.
Examples of preferable sensitizers include compounds belonging to the following compounds and having a maximum absorption wavelength in the 350 nm to 450 nm region. Polynuclear aromatics (eg pyrene, perylene, triphenylene, anthracene, phenanthrene), xanthenes (eg fluorescein, eosin, erythrosin, rhodamine B, rosebengal), xanthones (eg xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone) , 2-Isopropylthioxanthone, 2-chlorothioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, melocyanine, carbomerocyanine), rodocyanins, oxonors, thiadins (eg, thionin) , Methylcoumarin blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acryflavin, benzoflavin), acridones (eg, acridone, 10-butyl-2-chloroacrydone), anthraquinones (eg, anthraquinone, 9,10-Dibutoxyanthracene), squaryliums (eg, squarylium), styryls, basestyryls, coumarins (eg, 7-diethylamino-4-methylcoumarin, ketocoumarin), carbazoles (eg, N-vinylcarbazole) ), Kamferquinones, phenothiazines.
In addition, typical sensitizers that can be used in the present invention include those disclosed in Crivello [JV Crivello, Adv. In Polymer Sci., 62, 1 (1984)].
Preferred specific examples of the sensitizer include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthracene, coumarin, ketocoumarin, phenanthrene, camphorquinone. , Phenothiazines and the like.
Further, in the present invention, as the sensitizer, the compounds described in paragraphs 0043 to 0046 of Japanese Patent No. 4937806 and paragraphs 0036 of Japanese Patent Application Laid-Open No. 2011-3916 can also be preferably used.
When the sensitizer is contained in the curable composition for imprinting of the present invention, it is preferable to add the sensitizer at a ratio of 30 to 200 parts by mass with respect to 100 parts by mass of the photoradical polymerization initiator.
The sensitizer may be contained in only one kind or two or more kinds in the curable composition for imprint of the present invention. When two or more types are contained, the total amount is preferably in the above range.

<Release agent>
The type of the mold release agent used in the present invention is not particularly defined as long as it does not deviate from the gist of the present invention, but it is preferably added having a function of segregating at the interface with the mold and promoting the mold release from the mold. Means an agent. Specifically, it is a non-polymerizable agent having a surfactant and a polyalkylene glycol structure having at least one hydroxyl group at the terminal or having an etherified hydroxyl group and substantially free of fluorine atoms and silicon atoms. Examples thereof include compounds (hereinafter, may be referred to as “non-polymerizable compounds having releasability”).
The release agent may contain only one type, or may contain two or more types. When the release agent is contained, the total content is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, and even more preferably 2 to 5% by mass.

<< Surfactant >>
As the surfactant, a nonionic surfactant is preferable.
A nonionic surfactant is a compound having at least one hydrophobic portion and at least one nonionic hydrophilic moiety. The hydrophobic part and the hydrophilic part may be at the end of the molecule or inside, respectively. The hydrophobic portion is composed of a hydrophobic group selected from a hydrocarbon group, a fluorine-containing group, and a Si-containing group, and the number of carbon atoms in the hydrophobic portion is preferably 1 to 25, more preferably 2 to 15, and further 4 to 10. It is preferable, 5 to 8 is more preferable. The nonionic hydrophilic part includes an alcoholic hydroxyl group, a phenolic hydroxyl group, an ether group (preferably a polyoxyalkylene group or a cyclic ether group), an amide group, an imide group, a ureido group, a urethane group, a cyano group, a sulfonamide group, or a lactone group. It is preferable to have at least one group selected from the group consisting of a lactam group and a cyclocarbonate group. The nonionic surfactant may be a hydrocarbon-based, fluorine-based, Si-based, or fluorine-based or Si-based nonionic surfactant, but a fluorine-based or Si-based surfactant is more preferable, and a fluorine-based surfactant is preferable. Is even more preferable. Here, the "fluorine-based and Si-based surfactant" means a substance having both requirements of both a fluorine-based surfactant and a Si-based surfactant.
Commercially available fluorine-based nonionic surfactants include Florard FC-4430 and FC-4431 manufactured by Sumitomo 3M Co., Ltd., Surflon S-241, S-242, S-243 manufactured by Asahi Glass Co., Ltd., and Mitsubishi Materials Electronics Chemical Co., Ltd. EF Top EF-PN31M-03, EF-PN31M-04, EF-PN31M-05, EF-PN31M-06, MF-100, OMNOVA Polyfox PF-636, PF-6320, PF-656, PF-6520, Neos Surfactant 250, 251, 222F, 212M DFX-18, Daikin Industries Co., Ltd. Unidyne DS-401, DS-403, DS-406, DS-451, DSN-403N, DIC Megafuck F-430, F-444, F-477, F-553, F-556, F-557, F-559, F-562, F-565, F-567, F-569, manufactured by Megafuck Co., Ltd. Examples thereof include R-40, Capstone FS-3100 manufactured by DuPont, and Zonyl FSO-100.
When the curable composition for imprint of the present invention contains a surfactant, the content of the surfactant is preferably 0.1 to 10% by mass, and 0.2 to 5% by mass, based on the total composition excluding the solvent. By mass% is more preferable, and 0.5 to 5% by mass is even more preferable. The curable composition for imprint may contain only one type of surfactant, or may contain two or more types of surfactant. When two or more types are included, the total amount is preferably in the above range.

<< Non-polymerizable compound with releasability >>
The curable composition for imprint is a non-polymerizable compound having at least one hydroxyl group at the terminal or having a polyalkylene glycol structure in which the hydroxyl group is etherified and substantially free of fluorine atoms and silicon atoms. May include. Here, the non-polymerizable compound means a compound having no polymerizable group. Further, substantially free of fluorine atoms and silicon atoms means, for example, that the total content of fluorine atoms and silicon atoms is 1% by mass or less, and that the total content of fluorine atoms and silicon atoms is not contained at all. Is preferable. By having no fluorine atom and silicon atom, compatibility with the polymerizable compound is improved, and particularly in a curable composition for imprint that substantially does not contain a solvent, coating uniformity and pattern formation at the time of imprint are formed. Good properties and line edge roughness after dry etching.
As the polyalkylene structure contained in the non-polymerizable compound having releasability, a polyalkylene glycol structure containing an alkylene group having 1 to 6 carbon atoms is preferable, and a polyethylene glycol structure, a polypropylene glycol structure, a polybutylene glycol structure, or a polybutylene glycol structure thereof is used. A mixed structure is more preferable, a polyethylene glycol structure, a polypropylene glycol structure, or a mixed structure thereof is further preferable, and a polypropylene glycol structure is more preferable.
Further, the non-polymerizable compound may be composed substantially only of a polyalkylene glycol structure except for a terminal substituent. Here, substantially means that the components other than the polyalkylene glycol structure are 5% by mass or less of the whole, preferably 1% by mass or less. In particular, it is particularly preferable that the non-polymerizable compound having releasability contains a compound having substantially only a polypropylene glycol structure.
The polyalkylene glycol structure preferably has 3 to 100 alkylene glycol constituent units, more preferably 4 to 50 units, still more preferably 5 to 30 units, and 6 It is more preferable to have ~ 20 pieces.
The non-polymerizable compound having releasability preferably has at least one hydroxyl group at the terminal or the hydroxyl group is etherified. As long as it has at least one hydroxyl group at the terminal or the hydroxyl group is etherified, the remaining terminal may be a hydroxyl group, or the hydrogen atom of the terminal hydroxyl group may be substituted. As the group in which the hydrogen atom of the terminal hydroxyl group may be substituted, an alkyl group (that is, a polyalkylene glycol alkyl ether) and an acyl group (that is, a polyalkylene glycol ester) are preferable. Compounds having a plurality of (preferably two or three) polyalkylene glycol chains via a linking group can also be preferably used.
Preferred specific examples of the non-polymerizable compound having releasability are polyethylene glycol, polypropylene glycol (for example, manufactured by Wako Pure Chemical Industries, Ltd.), these mono or dimethyl ether, mono or dibutyl ether, mono or dioctyl ether, mono or disetyl. Ether, monostearic acid ester, monooleic acid ester, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, and trimethyl ethers thereof.
The weight average molecular weight of the non-polymerizable compound having releasability is preferably 150 to 6000, more preferably 200 to 3000, further preferably 250 to 2000, and even more preferably 300 to 1200.
Further, as the non-polymerizable compound having releasability that can be used in the present invention, a non-polymerizable compound having releasability having an acetylene diol structure can also be exemplified. Examples of commercially available non-polymerizable compounds having such releasability include Orfin E1010 (manufactured by Nisshin Chemical Industry Co., Ltd.) and the like.
When the curable composition for imprint of the present invention contains a non-polymerizable compound having releasability, the content of the non-polymerizable compound having releasability is 0.1 in all the compositions excluding the solvent. By mass% or more is preferable, 0.5% by mass or more is more preferable, 1.0% by mass or more is further preferable, and 2% by mass or more is further preferable. The content is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
The curable composition for imprint may contain only one type of non-polymerizable compound having releasability, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<Antioxidant>
The curable composition for imprinting of the present invention may contain an antioxidant. Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant.
Specific examples of the phenolic antioxidant are 2,6-di-t-butyl-4-methylphenol and n-octadecyl-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl. ) Propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4 , 4'-butylidene-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9- Bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] ] Undecan etc. can be mentioned.
Commercially available phenolic antioxidants include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 245, Irganox 259, Irganox 295, and Irganox 3114 (all of which are from BASF). Made by Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, and Adekastab AO-330 , All manufactured by ADEKA), Sumilyzer BHT, Sumilyzer BP-101, Sumilyzer GA-80, Sumilyzer MDP-S, Sumilyzer BBM-S, Sumilyzer GM, Sumilyzer GS (F), and Sumilyzer GP (all of which are Sumitomo Chemical). HOSTANOX O10, HOSTANOX O16, HOSTANOX O14, and HOSTANOX O3 (all manufactured by Clariant), ANTAGE BHT, ANTAGE W-300, ANTAGE W-400, and ANTAGE W500 (all manufactured by Kawaguchi Kagaku). SEENOX 224M and SEENOX 326M (all manufactured by Cipro Kasei Co., Ltd.), Yoshinox BHT, Yoshinox BB, Tominox TT, Tominox 917 (all manufactured by Yoshitomi Pharmaceutical Industries, Ltd.), TTHP (Manufactured by Toray Co., Ltd.) and the like.
Specific examples of phosphorus-based antioxidants include trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, and bis (2,4-di-t). -Butylphenyl) pentaerythritol phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphos Examples thereof include phyto, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene-di-phosphanite and the like. Commercially available phosphorus-based antioxidants include ADEKA STAB 1178 (manufactured by ADEKA Corporation), Sumilyzer TNP (manufactured by Sumitomo Chemical Co., Ltd.), JP-135 (manufactured by Johoku Chemical Co., Ltd.), and ADEKA STAB 2112 (manufactured by Johoku Chemical Co., Ltd.). ADEKA), JPP-2000 (Johoku Chemical Co., Ltd.), Weston 618 (GE), ADEKA STAB PEP-24G (ADEKA CORPORATION), ADEKA STAB PEP-36 (ADEKA CORPORATION), ADEKA STAB HP -10 (manufactured by ADEKA Corporation), SandstabP-EPQ (manufactured by Sand Co., Ltd.), Phosphite 168 (manufactured by BASF), and the like can be mentioned.
Specific examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, disstearyl-3,3'-thiodipropionate, and pentaerythritol. Tetrakis (3-laurylthiopropionate) and the like can be mentioned. Commercially available sulfur-based antioxidants include Sumilyzer TPL (Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (Yoshitomi Pharmaceutical Co., Ltd.), Antiox L (Nichiyu Co., Ltd.), and Sumilyzer TPM (Sumitomo Chemical Co., Ltd.). (Manufactured by Yoshitomi Pharmaceutical Co., Ltd.), Yoshinox DMTP (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), Antiox M (manufactured by Nichiyu Co., Ltd.), Sumilyzer TPS (manufactured by Sumitomo Chemical Co., Ltd.), Yoshinox DSTP (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) , Antiox S (manufactured by Nichiyu Co., Ltd.), ADEKA STAB AO-412S (manufactured by ADEKA Co., Ltd.), SEENOX 412S (manufactured by Cipro Kasei Co., Ltd.), Sumilyzer TDP (manufactured by Sumitomo Chemical Co., Ltd.), etc. ..
In addition, the antioxidant used in the examples described later can be preferably used.
When blended, the content of the antioxidant is preferably 0.001 to 5% by mass in the curable composition for imprinting. Only one type of antioxidant may be contained in the curable composition for imprinting, or two or more types may be contained. When two or more types are contained, the total amount is preferably in the above range.

<Other ingredients>
In addition to the above, the curable composition for imprint used in the present invention is a polymerization inhibitor (for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1) without departing from the spirit of the present invention. -Oxyl-free radicals, etc.), UV absorbers, solvents, etc. may be included. Each of these compounds may contain only one kind, or may contain two or more kinds. For details thereof, the description in paragraphs 0061 to 0064 of Japanese Patent Application Laid-Open No. 2014-170949 can be referred to, and these contents are incorporated in the present specification.

The curable composition for imprint of the present invention may have a content of a component having a weight average molecular weight of more than 2000 of 5% by mass or less, preferably 3% by mass or less, and 1% by mass. It is more preferably% or less, and even more preferably 0.1% by mass or less.

<Characteristics of curable composition for imprint>
The curable composition for imprinting of the present invention preferably has a viscosity at 25 ° C. of 15 mPa · s or less, more preferably 13 mPa · s or less, further preferably 11 mPa · s or less, and further preferably 9 mPa · s or less. Preferably, 8 mPa · s or less is even more preferable. The lower limit of the viscosity is not particularly specified, but can be, for example, 3 mPa · s or more, and further 5 mPa · s or more. Within such a range, the curable composition for imprinting of the present invention can easily enter the mold, and the mold filling time can be shortened. Further, it becomes possible to improve the pattern formation property and the throughput.

The Onishi parameter of the curable composition for imprint of the present invention is preferably 3.8 or less, more preferably 3.7 or less, further preferably 3.6 or less, further preferably 3.5 or less, and 3.4 or less. Is even more preferable. The lower limit of the Onishi parameter is not particularly specified, but can be, for example, equal to or higher than the above lower limit. By setting the Onishi parameter to the above upper limit value or less, the etching processing characteristics, particularly the pattern disconnection after etching can be suppressed more effectively.
The glass transition temperature of the curable composition for imprinting of the present invention after curing is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and even more preferably 150 ° C. or higher. The upper limit of the glass transition temperature is not particularly specified, but can be, for example, 350 ° C. or lower.

The curable composition for imprinting of the present invention may be filtered before use. For filtration, for example, a filter made of polytetrafluoroethylene (PTFE) can be used. The pore size of the filter is preferably 0.003 μm to 5.0 μm. For details of filtration, the description in paragraph 0070 of JP-A-2014-170949 can be referred to, and these contents are incorporated in the present specification.

As a storage container for the curable composition for imprint of the present invention, a conventionally known storage container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into raw materials and compositions, the inner wall of the container is made of a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are formed into a 7-layer structure. It is also preferable to use a bottle of resin. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

The curable composition for imprinting of the present invention is used as a photocured cured product. More specifically, it is used by forming a pattern by an optical imprint method.

<Pattern manufacturing method>
In the pattern manufacturing method of the present invention, the curable composition for imprint of the present invention is applied on a substrate or a mold, and the curable composition for imprint is irradiated with light in a state of being sandwiched between the mold and the substrate. including.
In the pattern manufacturing method of the present invention, a pattern is applied on a substrate or a mold. The method of application is not particularly specified, and the description in paragraph 0102 of JP-A-2010-109092 (corresponding US application is published in US Patent Application Publication 2011/199392) can be referred to, and these contents are incorporated in the present specification. .. In the present invention, the spin coating method and the inkjet method are preferable.
The substrate is not particularly specified, and the description of paragraph 0103 of Japanese Patent Application Laid-Open No. 2010-109092 (corresponding US application is published in US Patent Application 2011/199392) can be referred to, and these contents are incorporated in the present specification. Specifically, silicon substrate, glass substrate, sapphire substrate, silicon carbide (silicon carbide) substrate, gallium nitride substrate, metal aluminum substrate, amorphous aluminum oxide substrate, polycrystalline aluminum oxide substrate, GaAsP, GaP, AlGaAs, InGaN, GaN. , AlGaN, ZnSe, AlGaInP, or ZnO. Specific examples of the material of the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and bariumborosilicate glass.
In the present invention, a silicon substrate is preferable.
The mold is not particularly specified, and the description in paragraphs 0105 to 0109 of Japanese Patent Application Laid-Open No. 2010-109092 (corresponding US application is published in US Patent Application 2011/199392) can be referred to, and these contents are incorporated in the present specification. Is done. Quartz molds are preferred in the present invention. The mold pattern (line width) used in the present invention preferably has a size of 50 nm or less.

Then, the curable composition for imprint is irradiated with light in a state of being sandwiched between the mold and the substrate. The step of pressure contacting with the substrate or the mold can be preferably performed in a rare gas atmosphere, a reduced pressure atmosphere, or a reduced pressure rare gas atmosphere. Here, the decompressed atmosphere means a state in the space observed at a pressure lower than the atmospheric pressure (101325 Pa), and is preferably 1000 Pa or less, more preferably 100 Pa or less, still more preferably 1 Pa or less. When a rare gas is used, helium is preferable. The exposure amount is preferably in the range of ^{5 mJ / cm 2 to} 1000 mJ / cm ^2.
Here, it is preferable that the curable composition for imprinting of the present invention is further heated and cured after irradiation with light. Further, the underlayer film composition may be provided between the substrate and the curable composition layer for imprinting. That is, the curable composition for imprinting (and thus the cured product of the present invention) may be provided directly on the surface of the substrate or the mold, or may be provided on the substrate or the mold via one or more layers. May be good.
In addition to the above, for details of the pattern manufacturing method, the description in paragraphs 0103 to 0115 of JP-A-2010-109092 (corresponding US application is published in US patent application 2011/199392) can be referred to, and these contents are described in the present specification. Incorporated into the book.

The pattern manufacturing method of the present invention can form a fine pattern at low cost and with high accuracy by an optical imprint method (more preferably, an optical nanoimprint method). Therefore, what was formed by using the conventional photolithography technique can be formed with higher accuracy and lower cost. For example, the pattern in the present invention may be applied as a permanent film such as an overcoat layer or an insulating film used for a liquid crystal display (LCD), an etching resist for a semiconductor integrated circuit, a recording material, or a flat panel display. It is possible. In particular, the pattern obtained by the pattern manufacturing method of the present invention has excellent etching resistance and can be preferably used as an etching resist for dry etching using fluorocarbon or the like.

In permanent films (resists for structural members) used in liquid crystal displays (LCDs) and resists used in substrate processing of electronic materials, metal or organic ions in the resist are used so as not to interfere with the operation of the product. It is desirable to avoid mixing of sex impurities as much as possible. Therefore, the concentration of ionic impurities in the metal or organic substance in the curable composition for imprint used in the present invention is preferably 1 mass ppm (parts per million) or less, and 100 mass ppb (parts per billion) or less. More preferably, it is more preferably 10 mass ppb or less, and even more preferably 100 mass ppt or less.
As a method for removing ionic impurities of a metal or an organic substance from the curable composition for imprint, for example, filtration using a filter can be mentioned. The filter pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step.
Further, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. Examples thereof include a method of lining the inside of the apparatus with Teflon (registered trademark) and performing distillation under conditions in which contamination is suppressed as much as possible. The preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
In addition to filter filtration, impurities may be removed by an adsorbent, and filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.

<Pattern>
As described above, the pattern formed by the pattern manufacturing method of the present invention can be used as a permanent film used for LCDs and the like, and as an etching resist for semiconductor processing. Further, by using the pattern of the present invention to form a grid pattern on the glass substrate of the LCD, it is possible to inexpensively manufacture a polarizing plate having a large screen size (for example, 55 inches, more than 60 inches) with less reflection and absorption. Is. For example, the polarizing plates described in JP-A-2015-132825 and WO2011 / 132649 can be manufactured. In addition, 1 inch is 25.4 mm.
In addition, the permanent membrane is bottling, transported, and stored in a container such as a gallon bottle or a coated bottle after manufacturing. In this case, the inside of the container is replaced with inert nitrogen or argon for the purpose of preventing deterioration. You may leave it. Further, during transportation and storage, the temperature may be at room temperature, but in order to further prevent deterioration of the permanent film, the temperature may be controlled in the range of −20 ° C. to 0 ° C. Of course, it is preferable to block light at a level at which the reaction does not proceed.
Specifically, the pattern of the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state imaging element, a light emitting element such as an LED or an organic EL, an optical device such as an LCD, a diffraction lattice, a relief hologram, an optical waveguide, and the like. Optical components such as optical filters and microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizing plates, polarizing elements, optical films, flat panel display members such as pillars, nanobiodevices, immunoanalytical chips, deoxyribo It can be preferably used for producing a guide pattern for forming a fine pattern (directed self-assembury, DSA) using a nucleic acid (DNA) separation chip, a microreactor, a photonic liquid crystal display, and self-assembly of a block copolymer.

The pattern formed by the pattern manufacturing method of the present invention is also useful as an etching resist (mask for lithography). When the pattern is used as an etching resist, first, _{a silicon substrate (silicon wafer, etc.) on which a thin film such as SiO 2} is formed is used as the substrate, and the pattern manufacturing method of the present invention is used on the substrate, for example, nano. Alternatively, a micro-order fine pattern is formed. The present invention is particularly advantageous in that a nano-order fine pattern can be formed, and a pattern having a size of 50 nm or less, particularly 30 nm or less can be formed. The lower limit of the size of the pattern formed by the pattern manufacturing method of the present invention is not particularly specified, but can be, for example, 1 nm or more.
After that, a desired pattern can be formed on the substrate by etching with an etching gas such as hydrogen fluoride in the case of wet etching and CF _{4 in the case of dry etching.} The pattern has particularly good etching resistance to dry etching. That is, the pattern obtained by the production method of the present invention is preferably used as an etching mask. The present invention also discloses a method for manufacturing a substrate to be processed, which is etched using the pattern obtained by the manufacturing method of the present invention as a mask.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Ｎ_２フローしている５Ｌの三口フラスコに３−クロロプロピオニルクロリド（3-Chloropropionyl Chloride）１５８．５ｇ（１．２５ｍｏｌ）、アセトニトリル０．１Ｌを加え、−１０℃に冷却した。ネオペンチルグリコール５９．４ｇ（０．５７ｍｏｌ）と、ジメチルアセトアミド１２２．１ｇ（１．４０ｍｏｌ）とアセトニトリル０．１Ｌを混合した混合物を上記三口フラスコの内温が０℃を超えない温度で２時間かけて滴下し、さらに０℃で２時間熟成を行った。その後、−１０℃まで冷却し、蒸留水０．５Ｌを上記三口フラスコの内温が０℃を超えない温度で０．５時間かけて滴下した。さらに、酢酸エチル２．０Ｌを加え、激しく３０分間撹拌した。その後、静止して水層を除去し、蒸留水１．０Ｌを加え、激しく３０分間撹拌した。その後、静止して水層を除去し、１ＭのＨＣｌを１．０Ｌ加え、激しく３０分間撹拌した。その後、静止して水層を除去した。得られた有機層を減圧濃縮することで化合物（Ｇ−９Ａ）を得た。 <Synthesis example>
<< Intermediate G-9A >>

158.5 g (1.25 mol) of 3-Chloropropionyl Chloride and 0.1 L of acetonitrile were added to a 5 L three-necked flask with N _{2 flow, and the mixture was cooled to −10 ° C.} A mixture of 59.4 g (0.57 mol) of neopentyl glycol, 122.1 g (1.40 mol) of dimethylacetamide and 0.1 L of acetonitrile was mixed over 2 hours at a temperature at which the internal temperature of the three-necked flask did not exceed 0 ° C. Was added dropwise, and the mixture was further aged at 0 ° C. for 2 hours. Then, the mixture was cooled to −10 ° C., and 0.5 L of distilled water was added dropwise over 0.5 hours at a temperature at which the internal temperature of the three-necked flask did not exceed 0 ° C. Further, 2.0 L of ethyl acetate was added, and the mixture was vigorously stirred for 30 minutes. Then, the aqueous layer was removed at rest, 1.0 L of distilled water was added, and the mixture was vigorously stirred for 30 minutes. Then, the aqueous layer was removed at rest, 1.0 L of 1 M HCl was added, and the mixture was vigorously stirred for 30 minutes. After that, the aqueous layer was removed at rest. The obtained organic layer was concentrated under reduced pressure to obtain a compound (G-9A).

<< Intermediate G-9 >>
Add 50 g (0.18 mol) of G-9A, 38 g (0.18 mol) of light acrylate NP-A manufactured by Kyoeisha Chemical Co., Ltd., and 0.2 L of acetonitrile to a ₂ L three-necked flask with N 2 flow, and bring to -10 ° C. Cooled. 13 g (0.18 mol) of diethylamine was added dropwise over 2 hours at a temperature at which the internal temperature of the flask did not exceed 0 ° C., and further aging was carried out at 0 ° C. for 5 hours. Then, the mixture was cooled to −10 ° C., and 0.5 L of distilled water was added dropwise over 0.5 hours at a temperature at which the internal temperature of the flask did not exceed 0 ° C. Further, 2.0 L of ethyl acetate was added, and the mixture was vigorously stirred for 30 minutes. Then, the aqueous layer was removed at rest, 1.0 L of distilled water was added, and the mixture was vigorously stirred for 30 minutes. After that, the aqueous layer was removed at rest. The obtained organic layer was concentrated under reduced pressure and purified by silica gel chromatography to obtain compound (G-9).

G-9

<G-1 to G-7 and G-9 to G-40>
Following the above G-9, G-1 to G-7 and G-9 to G-40 were also synthesized.

Examples and Comparative Examples <Preparation of curable composition for imprint>
As shown in Tables 2 to 4 below, each compound (compound numbered A, B, C, D, G in the table) is mixed, and 4-hydroxy-2, as a polymerization inhibitor, is further added. 200 mass ppm (0) of 2,6,6-tetramethylpiperidin-1-oxyl-free radical (manufactured by Tokyo Kasei Co., Ltd.) with respect to 100 mass% of the polymerizable compound (total amount of A, B, G compounds in the table). It was added so as to be 0.02% by mass). This was filtered through a filter made of polytetrafluoroethylene (PTFE) having a pore size of 0.1 μm to prepare a curable composition for imprinting. The blending amount of each component in Tables 2 to 4 is a mass ratio.
The obtained curable composition for imprint was evaluated as follows. The results are shown in Table 5.

<Viscosity>
The viscosity of the curable composition for imprint (before curing) and the polyfunctional radical polymerizable compound was measured at 25 ° C. using a RE-80L type rotational viscometer manufactured by Toki Sangyo Co., Ltd.
The rotation speed at the time of measurement is as shown in Table 1 below according to the viscosity.

実施例１〜４３のインプリント用硬化性組成物の粘度（２５℃）を上記測定条件に従って測定した結果、３〜１５ｍＰａ・ｓの範囲にあることを確認した。

As a result of measuring the viscosity (25 ° C.) of the curable composition for imprint of Examples 1 to 43 according to the above measurement conditions, it was confirmed that the viscosity was in the range of 3 to 15 mPa · s.

<Adhesion>
The adhesion between the substrate and the cured product for imprinting was evaluated as follows.
An imprintable curable composition of Examples and Comparative Examples whose temperature was adjusted to 25 ° C. was applied to the surface of SOC (Spun On Carbon) formed on a silicon wafer using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics. Then, the droplets were discharged at a droplet amount of 1 pl per nozzle, and the droplets were applied onto the adhesive film so as to form a square arrangement at intervals of about 100 μm.
From the top, a quartz mold having a line width of 30 nm and a depth of 60 nm / space is placed so as to be in contact with the curable composition layer for imprinting, and 300 mJ / cm from the quartz wafer side using a high-pressure mercury lamp. ^It was exposed under the condition of 2. After the exposure, the quartz mold was released, and the peeled area% at that time was measured.
This peeled area% corresponds to the adhesion force F (unit: N).
A: Peeled area ≤ 1%
B: 5%> Peeled area> 1%
C: Peeled area ≥ 5%
<Release force>
As the quartz mold, a quartz mold having a line width of 30 nm and a depth of 60 nm with a line / space was used. The curable composition for imprint was applied onto a silicon wafer by an inkjet method using an inkjet printer DMP-2831 manufactured by FUJIFILM Dimatix as an inkjet device, and then sandwiched between the molds in a helium atmosphere. A high-pressure mercury lamp was used to ^{expose the quartz mold surface under the condition of 100 mJ / cm 2} , and the quartz mold was released to obtain a pattern having a pattern size (line width) of 30 nm (hereinafter referred to as a sample). The thickness (pattern height) of the residual film of the sample was 60 nm. In addition, the force required for mold release (release force F) at that time was measured.
Evaluation was made according to the following evaluation categories.
A: F ≦ 12N
B: 12N <F ≦ 18N
C: F> 18N

<Storage stability>
After the curable compositions for imprint of Examples and Comparative Examples were placed in an atmosphere of 40 ° C. for 1 week, the rate of decrease in the purity of the simple substance in the composition was measured, and the total rate of decrease in them was defined as the stability. ..
Evaluation was made according to the following evaluation categories.
A: Total reduction rate ≤ 1%
B: 5%> Total decrease rate> 1%
C: Total reduction rate ≥ 5%

The compounds used in Tables 2 to 4 are as follows. The compounds represented by the formula (1) are the compounds exemplified above by the numbers of GX (X is an ordinal number, the same applies hereinafter) except for G-1-13 and G-1-14. The compounds represented by the formula (2) are the respective compounds exemplified above by the numbers BX, except for B-1-13 and B-1-14. The monofunctional radically polymerizable compounds are the compounds shown in Table 6 below as numbers AX. The photoradical polymerization initiator is a compound shown in Table 7 below as a CX number. The release agent is a compound shown in Table 8 below as a DX number.

大西パラメータは、下記式より算出した。
大西パラメータ＝（Ｃ、Ｈ、およびＯの原子数の和）／（Ｃ原子数−Ｏ原子数）

The Onishi parameter was calculated from the following formula.
Onishi parameter = (sum of atomic numbers of C, H, and O) / (number of C atoms-O atomic number)

As is clear from Table 5 and the like above, in the curable composition for imprint of the present invention, the cured product was excellent in adhesion to the substrate, and the curable composition for imprint itself was excellent in storage stability.
Further, the curable composition for imprint of the present invention was also excellent in mold releasability.
Further, from this result, the curable composition for imprint of the present invention can be used as a material for a cured product and a pattern used for various purposes, and the cured product and the pattern are particularly suitable as a mask for lithography. You can see that it is available.
On the other hand, the curable composition for imprint of the comparative example containing no compound represented by the formula (1) is inferior in the adhesion of the cured product to the substrate and the storage stability of the curable composition for imprint. Was there.

Claims (19)

A curable composition for imprint containing a compound represented by the following formula (1), a radically polymerizable compound other than the compound represented by the above formula (1), and a photoradical polymerization initiator;

In formula (1), R ¹ and R ² are independent hydrogen atoms or organic groups having 1 to 8 carbon atoms, and may be bonded to each other to form a ring; R ³ is monovalent. is an organic group; ^{R 4} and ^{R 5} are each independently, Ri hydrogen atom or a monovalent organic group der, ^{R 4} or ^{R 5} is an organic group represented by the following formula (1-3);

In formula (1-3), R ⁶ represents a monovalent organic group; * represents the bond position. R of the above formula (1) ³ And R of the above formula (1-3) ⁶ The curable composition for imprint according to claim 1, wherein each of them is independently represented by the following formula (1-1);

It contains a compound represented by the following formula (1), a radically polymerizable compound other than the compound represented by the above formula (1), and a photoradical polymerization initiator.
The content of the compound represented by the formula (1) is 0.005 to 1 part by mass with respect to 100 parts by mass of the content of the radically polymerizable compound other than the compound represented by the formula (1). , Curable composition for imprint.

In equation (1), R ¹ And R ² Are independently hydrogen atoms or organic groups having 1 to 8 carbon atoms and may be bonded to each other to form a ring; R. ³ Is a monovalent organic group; R ⁴ And R ⁵ Are independently hydrogen atoms or monovalent organic groups. The curable composition for imprint according to any one of claims 1 to 3, wherein the radically polymerizable compound other than the compound represented by the formula (1) contains at least one (meth) acryloyl group. .. The curable composition for imprint according to any one of claims 1 to 4 , wherein the compound represented by the formula (1) has a molecular weight of 100 to 1500. The curable composition for imprint according to any one of claims 1 to 5 , wherein the compound represented by the formula (1) has a radically polymerizable group. The imprint according to any one of claims 1 to 6 , wherein at least one radically polymerizable compound other than the compound represented by the formula (1) contains a compound represented by the following formula (2). Curable composition for use;

In formula (2), R ²¹ is a q-valent organic group, R ²² is a hydrogen atom or a methyl group, and q is an integer of 2 or more. The curability for imprint according to any one of claims 1 to 7 , wherein at least one of the radically polymerizable compounds other than the compound represented by the formula (1) is a monofunctional (meth) acrylic monomer. Composition. The curable composition for imprint according to any one of claims 1 to 8 , wherein the content of the solvent in the curable composition for imprint is 5% by mass or less. The curable composition for imprint according to any one of claims 1 to 9 , wherein the content of the component having a weight average molecular weight of more than 2000 in the curable composition for imprint is 5% by mass or less. The curable composition for imprint according to any one of claims 1 to 10 , wherein the curable composition for imprint has a viscosity of 3 to 15 mPa · s at 25 ° C. A cured product formed from the curable composition for imprint according to any one of claims 1 to 11. The cured product according to claim 12 , wherein the cured product is provided on a silicon substrate. A state in which the curable composition for imprint according to any one of claims 1 to 11 is applied on a substrate or a mold, and the curable composition for imprint is sandwiched between the mold and the substrate. A pattern manufacturing method including irradiating with light. The pattern manufacturing method according to claim 14 , wherein the size of the pattern is 30 nm or less. A method for manufacturing a substrate to be processed, wherein etching is performed using the pattern obtained by the pattern manufacturing method according to claim 14 or 15 as a mask. A pattern formed from the curable composition according to any one of claims 1 to 11, wherein the pattern size is 30 nm or less. An etching mask comprising at least one of the patterns according to claim 17. A polymerizable composition for imprint containing a compound represented by the following formula (1) and a compound represented by the following formula (2);

In formula (1), R ¹ and R ² are independent hydrogen atoms or organic groups having 1 to 8 carbon atoms, and may be bonded to each other to form a ring; R ³ is monovalent. is an organic group; ^{R 4} and ^{R 5} are each independently, Ri hydrogen atom or a monovalent organic group der, ^{R 4} or ^{R 5} is an organic group represented by the following formula (1-3);

In formula (1-3), R ⁶ represents a monovalent organic group; * represents a bond position;

In formula (2), R ²¹ is a q-valent organic group, R ²² is a hydrogen atom or a methyl group, and q is an integer of 2 or more.